The accurate measurement of plasma potentials at high pressure is investigated with the emissive probe. The emissive probe I-V characteristic of argon plasma obtained at 100 Pa is interpreted in detail, showing two inflection points in the I-V trace. The accurate plasma potentials at high pressure can be determined from the first inflection point potentials (the higher potential) by the improved inflection point method of the emissive probe, while the second inflection point is a result of the additional ionizing phenomenon caused by the collision between the emitted electrons and the neutral argon atoms. Besides, the accuracy of the plasma potential measurement at high pressure is verified to be 0.3 V by the measurement of space potential distribution between two parallel plates in neutral gas at 100 Pa. The accurate measurement of space potentials in high pressure plasma and neutral gas indicates that the improved inflection point method of the emissive probe is promising in the study of collisional sheath structures and the electrostatic probe diagnostic of high pressure plasmas.